US3376335A

US3376335A - Carbamic acid esters

Info

Publication number: US3376335A
Application number: US423596A
Authority: US
Inventors: Goliasch Karl; Pelster Heinrich; Muhlbauer Ernst; Heiss Rudolf; Scheinpflug Hans
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1964-01-25
Filing date: 1965-01-05
Publication date: 1968-04-02
Anticipated expiration: 1985-04-02
Also published as: ES308529A1; ES310863A1; GB1025049A; NL6500915A; IL22692A; FR1452615A; CH441861A; BE658752A

Description

United States Patent 5 Claims. (Ci. 260-479) The present invention relates to new ca-rbamic acid esters which have fungitoxic properties, and to a process for the production thereof.

One object of the present invention consists in disclosing new carbamic acid esters which have fungitoxic properties. Another object consists in providing several processes for the production of these new carbamic acid esters. It is also an object of the invention to provide new agents for combating phytopathogenic fungi. Further objects can be seen from the following description and the examples.

It is already known that substituted phenyl-N-,N-dimethyl carbamates have herbicidal properties (cf. U.S Patent No. 3,933,383), but a fungicidal activity of these substances has hitherto not been known.

It has been found that the new carbamic acid esters of the formula in which:

R; stands for hydrogen, alkyl, alkenyl, alkox'y, dialkylamino, dialkenylamino, alkylmercapto, alkenylmercapto, halogen and/or nitro,

A stands for alkylene with 1 to carbon atoms,

R stands for chlorine, alkoxy, alkylmercapto, cycloalkoxy or a 'heterocyclic radical, and

n stands for a number from 1 to 5,

have strong fungitoxic properties.

It has also been found that the carbamic acid esters of the Formula I are obtained when, in a manner known as such,

(a) phenols of the general formula H NAR in which A and R have the above meaning, or

(c) phenols of the Formula II are converted in a first step with phosgene into the corresponding bis-phenyl carbon-ates, and these are reacted in a second step with amines of the Formula IV.

If, for example, 2,4-dichloro-fi-nitro-phenol and l-isocyanato-6-chloro-n-hexane are used as starting materials, the course of the reaction can be illustrated by the following reaction scheme:

The starting materials to be used are clearly characterised by the above Formulae II, III, and IV. In these formulae, R preferably stands for hydrogen, alkyl, alkenyl, alkoxy, dialkylamino and alkylmercapto, each with 1 to 4 carbon atoms in the alkyl radicals, for dialkenylamino and alkenylmercapto, each with 2 to 4 carbon atoms in the alkenyl radicals, as well as for chlorine, bromine and nitro. A chiefly stands for alkylene with 1 to 8 carbon atoms. R preferably stands for chlorine, alkoxy with 1 to 10 carbon atoms, alkylmercapto with 1 to 4 carbon atoms, cycloalkoxy with 5 to 6' ring atoms and heterocyclic radicals with 5 to 6 ring atoms which preferably contain oxygen, nitrogen or sulphur.

As examples of phenols which can be used according to the invention, there may be mentioned: phenol, 4-. methyl-, 3-methyl-4-chloro-, 2-allyl-, 3-methoxy-, 2- ChlOI'Or, 3-chloro-, 4-chloro-, 2,4-dichloro 2,4-dichloro-, 6-nitro-, 2,4,6-tri'chloro-, pentachloro, 2-chlo1ro4-nitro-, 3-methyl-4-dimethylamino-, 2-diallylamino-, 4-methylmercapto 3amethyl-4-methylmercapto-, 3,5-dimethyl-4- methylmercapto-, 2-isopropyl-4-methylmercapto-, 3-lmethyl-4-allylmercapto-phenol.

Examples of isocyanates or amines to be used according to the invention are l-chloroethyl-2-, l-chlorobutoxypropyl-, 1-chloro-n-'hexyl-6-, methoxymethyl-, methoxypropyl-, ethoxypropyl-, sec. buto-xypropyl-, cyclohexoxypropyl-, -isopropyloxypropyl-, 2-ethylhexoXypropyl-, methylmercaptoethyl-, ethylmercaptopropyl-isocyanate or -amine.

The process (a) is expediently carried out in the presence of inert organic solvents within a temperature range between -50 and +150 C., and bases, preferably tertiary amines such as triethylamine and pyridine, are optionally added as catalysts.

The first step of process (b) is expediently carried out at pH values below 6 in aqueous or alcoholic solvents Within a temperature range between about 50 and +150 C. The second step of this process is expediently performed in the presence of inert organic solvents within a temperature range of about 20 to C.

The first step of process (c) is expediently carried out at pH values between 6 and 9 in the presence of inert organic solvents, with the addition of an inorganic agent splitting off acid, such as a sodium hydroxide solution, at temperatures between and 100 C. The second step of this process is expediently performed in the presence of inert organic solvents at temperatures between 50 and 150 C.

Suitable inert organic solvents are, for example, hydrocarbons, such as benzine and benzene; chlorinated hydrocarbons, such as methylene chloride and dichlorobenzene; ethers, such as diethyl ether and dioxan; ketones, such as acetone and cyclohexanone, as well as acetonitrile and dimethyl formamide. However, it is also possible to work without a solvent.

For carrying out the processes according to the invention, the reaction components are used in about equimolar amounts, but the phosgene can also be employed in excess. The reaction is carried out in the, usual manner. Working up is performed by known methods;

The compounds according to the invention have a strong fungitoxic effect and are distinguished by a broad spectrum of activity. Due to their low toxicity towards warm-blooded animals, they are suitable for combating undesirable fungus growth. Their good compatibility with higher plants enables them to be used as plant protective agents against fungus diseases.

The compounds according to the invention have proved especially satisfactory for controlling rice diseases. They have an excellent protective effect when combating Piricularia oryzae in rice.

They also have a good fungitoxic activity against other fungi causing rice diseases, such as Cochliobolus miyabeanus and Corticium sasakii.

The substances according to the invention also have an especially good activity against a number of other fungi, such as species of Mycosphaerella, Cercospora, Corticium, Alternaria, Septoria, and against Botrytis cinerea.

The compounds according to the invention also have a fungitoxic acivity against fungi which attack the plant from the soil and sometimes cause tracheomycoses, such as Phz'alophora cinerescens, Verticillium alboatrum, Fusarizzm oxysp.f.cubense, Fusarium oxysp.f.dianthi.

Since the compounds according to the invention, as leaf fungicides, have mainly a protective effect, a mixture with curative agents is advantageous. Organic mercury compounds, such as phenyl-mercury acetate, and also antibiotics, such as Plasticidin S, are suitable for this purpose. By adding the compounds according to the invention, a substantial reduction of the mercury content can be achieved in the mixed preparation. The disadvantages occurring when organic mercury compounds are used by themselves, such as the toxicity towards warm-blooded animals, can thus be reduced. By combining preparations of protective and of curative effect, as in the mixture mentioned above, an increased effectiveness can be attained.

The compounds according to the invention can be transformed into the usual formulations, such as emulsifiable concentrates, spray powders, pastes, soluble powders, dusts and granulates. These are prepared in known manner, for example by extending the active ingredients with solvents and/ or carriers, if desired with the use of emulsifiers and/or dispersing agents (cf. Agricultural Chemicals, March 1960, pages 35-38). Suitable auxiliaries for this purpose are mainly solvents, such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g. ethanolaminq'dimethyl formamide), and water; carriers, such as natural rock flours (e.g. kaolins, aluminas, talc, chalk), and ground synthetic stone (e.g. highly dispersed silicic acid, silicates); emulsifiers, such as non-ionic and anionic emulsifiers (e.g. polyoxyethylenefatty acid esters, polyoxyethylene-fatty alcohol ethers, alkylsulphonates and arylsulphonates), and dispersing agents, such as lignin, sul.

phite waste liquors and methyl cellulose.

The compounds according to the invention can be pres ent in the formulations in admixture with other known active ingredients.

The formulations generally contain between 0.1 and 95, preferably between 0.5 and 90, percent by weight of active compound.

The compounds to be used or their preparations are applied in usual manner, for example by spraying, dusting, sprinkling or atomizing. The active ingredient can be used in concentrations between 0.2 and 0.005%, dependent upon the intended application. In special cases, however, it is possible to exceed or to remain below this range of concentration.

The following examples are given for the purpose of illustrating the invention:

Example A.-Piricularia test/ liquid preparation of active compound Solvent: 1 part by weight of acetone Dispersing agent: 0.05 part by weight sodium oleate Other additives: 0.2 part by weight gelatin Water: 98.75 parts by weight H O The amount of active compound required for the desired concentration of the active compound in the spray liquid is mixed with the stated amount of solvent, and the concentrate obtained is diluted with the stated amount of water containing the stated additives.

Thirty rice plants which are about 14 days old, are 1 sprayed with the spray liquid until dripping wet. The plants remain in a greenhouse at temperatures of 22 to 24 C. and at a relative atmospheric humidity of about until dry. They are then inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml. of Piricularia oryzae and placed in a room-at 24-26 C. and at a relative atmospheric humidity of Five days after inoculation, the infestation of all the leaves of the treated plants, which were present at the time of inoculation, are determined as a percentage of the untreated, but also inoculated control plants. 0% means that no infestation occured, 100% means that the infestation is exactly the same as that of the control plants. The active compounds, their concentrations and the results obtained can be seen from the table below (Table 1). 5

Example B.Piricularia test/solid preparation of active compound Solvent: 10 parts by weight acetone Dust Base: 100 parts by weight 0.5% Mg. stearate 4.0% silicic acid 0.5% Mg. stearate Piricularz'a, oryzae and placed in a room at 2426 C.

and at a relative atmospheric humidity of 100%.

Five days after inoculation, the infestation of all the leaves of the treated plants, which were present at the time of inoculation, are determined as a percentage of, the untreated, but also inoculated control plants. 0%

means that no infestation occurred, and 100% means that the infestation is exactly the same as that of the control plants.

The active compounds, theirconcentrations and the results obtained can be seen from the following table.

:E s o 034 12 TABLE 2.Continucd 04 0002 r .QEES Esr e m m m m m m m m m w m w w 32 m l 6 a y C @256 EEEEE 0024. 14 m m 004 m 04 m m 0003 MM m E 3 \N S 0001 02 mm 0002 01m 0001 mm P m m n v d O C d n 6 0004 03 0004 04. n n 0003 A S M mm m u W g E Q Q n n n H e n O 0 353: 0 6 C m I 0 O h 33% 000 00 n F 0002 00 U 0001 v n 1 1 m a C P 4 C 0 C r. :1 2 3 0024 24. n u 004 n 04 u 0004 T m .h h e.mfl 0 d 1 52? u n n m h w m m n m W 3.858 0013 14 n n 004 04. n u 0003 m w 3 H m .w M 23 I n I mh E w m mmmm m 4 t I u E w ec 0000 02 n u 0000 02 u n 0002 m D m 5 L u w W M EREEU I I HIWCh P H W W W t t V r HWLNN MMWMWO 0001 01 m m 0001 01 U m 0000 W mm m mub m Pi l 0 58.5.3.5. 0001 00 u n 0004 04 n n 0002 S W n S EQ QEQ n u .1 010i 1 E O ".m 83m M w .1 t. e fi 0003 14 u u 004 n 03 n n 000 2 4 H O a C W 5222 6 I u I e a v.8) 1 o m s e n. a 3 M C N H ll W T 0001 02 004 04 0002 1 2L 6 O S p 53.5350 n I m m Ob .wwo m @593 0001 12 m m 0003 03 m m 0001 1 m f g m f. m 3.5282 O 2 e 2 a PH 8 a rd, e m m 1 m mm mm 0 d C n h f 0 d m H 1 PO 6 Y 20 1 C 6 .m 1.1f 1.1 u h 0 a S e M m 0000 0000 0000 0000 0000 .m. r Y H 10 T rm 0051 0051 O 51 mo mfil 0051 u a m 0 H mwm 51 51 5 51 cnt. C .mmwaflfi 6 V 5 O 5 Ofi 5 5 Co a 0 6 B .l. S 0d bh W "m h nb N m n m 2 h n 6 w a U .m C w a rk u m 5 a H V 6 0d r 0 w \l C B e H 2 .l. n t S w H m wk wm l) C .B 0 a vfl a d r 0 U P m n n H a P e m s e 0 C C C 0 e O I 1 I I m m mm a w a o P m m m o m 0 h f eh@ m w. m 1 o 1 m .m4 m t m 2 n h C \n i E n a d e l 1 2 O C 6 .l E O S I L r I h y W H H H I h B 1 0 e t P L d w w m c w m m w n .1 m P n 2 u n n l ma ,1. o m M o o H C H C H0 1 2 0 m 0 p H h C o n%.m m v N N N c a u a6 o H H E o i 4 h .3 E w o N o N 0 M t a a 1 4 9 m J o 4 w 4 m 2, w a w m O A 4 o w o w m m m m 3 1 m m m n w t c N a m w o n m ah mm o 0 r. S V S H r. a 6 .1 6 m m m dfl: w C 3 ad P 5 m W .m m 0 $6 0 6 l .1 4 m w th W .1 lo 1 C l L m hm C m C C C m 0 m CM propoxy-propylamine are added dropwise at 0 to +15 C. After further stirring for 4 hours, the reaction solution is poured into water, the benzene is separated, washed once with 100 ml. of 1 N NaOH and twice with 100 ml. of water, then dried and concentrated.

Yield of 2,4-dichloro-fi-nitro-phenyl-N-(3-isopropoxypropyl) carbamate: 48.5 g. (92.0% of the theoretical), oluene, in such a manner 79-80) 0 EXAMPLE 4 that the phenolic solution is adde responding chloroformie acid In analogy with the methods described above, the foll t d, i i i canlowing carb'arnic acid esters are obtained in good yields:

hosgene is re- (1) C1 moved in a vacuum. After the mixture is filtered off with 01 OG""NH(CH2)GCl 2,4 dichlorophenyl N-(6-chloro-n -hexyl) carbamatet 73 MP. 55-56 c.

(31- O(I ]}NH-(CH2)30C2H5 N02 A solution of 20.8 g. of 2,4-dichloro-6-nitro-phenol in 150 ml. of toluene, and a solution of 11 g. of triethylamine in ml. of toluene are simultaneously added dropwise at 5-10 C., While stirring, to a solution of 10 g. of p-hosgene in 50ml. of t d more rapidly. The corphenyl ester is formed. When the dropwise addition is comp tinued for 30 minutes, and the excess p suction from the precipitated salt, a solution of 20.8 g. of ethoxypropylamine in 50 ml. of toluene is 'added dropwise at room temperature. After further stirring for two hours and filtering off the ethoxypropylamine hydro- 2,4 dichloro 6 nitro phenyl N (Z-chloro-et-hyl) carbamate; M.P. 142 C.

2,4,6-trichloro-phenyl N [3-(Z-methyD-cyclohexoxypropyl] carbamate; M.P. 61 C.

3,5-dimethyl 4 allylmercapto-phenyl N (Z-methylmercapto-ethyl) carbamate; M.P. 45 C.

wherein D is alkylene of l-8 carbon atoms and R is a member selected from the group consisting of alkoxy of 1-10 carbon atoms, chloro, cycloalkoxy of 56 carbon atoms in the ring, alkyl mercapto of 1-4 carbon atoms and 12 2. The compound of the formula D is allzylene of 18 carbon atoms; and R is alkoxy of 1-l0 carbon atoms. 3. The compound of the formula 4. The carbamic acid ester of the formula 5. The carbamic acid ester of the formula References Cited UNITED STATES PATENTS 7/1960 Jones et al. 167-30 X 4/1964 Surrey et al. 260-479 9/1965 Heiss et al. 260-479 FOREIGN PATENTS 5/1963 Belgium. 11/1962 Germany.

OTHER REFERENCES Iwakura et al.: Journalof Organic Chemistry, vol. 26, pp. 43844388 (1966), QD241 J6.

LORRAINE A. WEINBERGER, Primary Examiner. RICHARD K. JACKSON, Examiner.

I. PELLMAN, M. WEBSTER, Assistant Examiners.

Claims

1. A COMPOUND OF THE FORMULA